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Notes for NET & SET - Chemical Sciences

CHAPTER NO. 7 : CONCEPT OF CHIRALITY (STEREOCHEMISTRY)

BASIC TERMS

1) Anti conformation :
For example, anti conformation of butane, two methyl groups at an angle of 180 to each
other.
CH 3

CH3

2) Chair conformation :
Staggered conformation of cyclohexane that has no angle strain or torsional strain and is
therefore lowest energy conformation.

3) Chiral molecule :
A molecule that is not superimposable on its mirror image. Chiral molecules have
handedness and are capable of exisiting as a pair of enantiomers.
4) Chirality :
The property of having handedness.
5) Configuration :
The particular arrangement of atoms or groups in space that is characteristic of a
given stereoisomer.
6) Conformation :
A particular temporary orientation of a molecule that results from rotations about
its single bond.
7) Conformational analysis :
An analysis of the energy changes that a molecule undergoes as its groups undergo
rotations(sometimes only partial) about the single bonds that join them.
8) Conformer :
A particular staggered conformation of a molecule.
9) Dextrorotatory :
A compound that rotates plane palarised light clockwise.

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10) Diastereomers :
Stereoisomers that are not mirror image of each other.

11) Eclipsed conformation :


A temporary orientation of grups around two atoms joined by a single bond such
that the groups directly oppose each other.

12) Gauche conformation :


A gauche conformation of butane, for example, in which methyl groups at an angle of 60
to each other.
CH3
CH 3

13) Isomers :
Different molecules that have the same molecular formula.
14) Mutarotation :
The spontaneous change that takes place in the optical rotation of & anomers
of a sugar when they are dissoved in water. The optical rotations of the sugars change until
they reach the same value.
15) Plane polarised light :
Ordinary light in which the oscillations of the electrical field occur only in one
plane.
16) Racemic form (recemic mixture) :
An equimolar mixture of enantiomers. A racemic form is optically inactive.
17) Meso compound :
An optically inactive compound whose molecules are achiral even though they
contain tetrahedral atoms with four different attached groups.
18) Optically active compounds :
A compound that rotates the plane of polarisation of plane polarised light.
19) Periplaner :
A conformation in which vicinal groups lie in the same plane.

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20) Staggered conformation :


A temporary orientation of groups around two atoms joined by a single bond such that
the bonds of the back atom exactly bisect the angles formed by the bonds of the front atom in
Newman projection formula.
21) Resolution :
The process by which the enantiomers of the racemic forms are separated.
22) Rotamers :
Rotamers are extreme conformations.
23) Homomers :
Identical representation of same compound.

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Notes for NET & SET - Chemical Sciences

STEROISOMERISM

Stereochemistry deals with the study of arrangement of atoms of a molecule in


three diamension space.
Stereoisomers are the compounds that have same molecular formula and mode of
attachment between atoms but differ in arrangement of atoms in space. This phenomenon
is called stereoisomerism. Stereoisomerism is of three types :
1) Conformational isomerism
2) Optical isomerism
3) Geometrical isomerism.

CONFORMATION ISOMERISM

Groups bonded only by a sigma bond (i.e.by a single bond) can undergo rotation
about that bond with respect to each other. That is, these groups are not fixed in a single
position, but are relatively free to rotate about the single bond connecting them. The
different structures which result by rotation about a sigma bond are called as conformations.
Conformational stereoisomers interconvert easily at room temperature through
rotation about single bond.
A single conformation cannot be physically separated from one another.

METHODS OF REPRESENTING CONFORMATIONS


Three diamensional figures cannot be properly represented on a two diamensional
surface like that of paper. Hence various projectional formulae have been suggested for
drawing conformations. Four of them are discussed below:
1) Dotted line wedge formula :
Dotted line wedge formula is a shorthand notation used to simplify three
diamensional drawing. In this method the molecule is seen from the side of C C bond.
1) Dashed lines show the bonds that go backward away from the reader.
2) Thick lines are used to show bonds that come forward, towards the reader.
3) The normal lines represent bonds within the plane of the paper.

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A plane drawn through the H-C-H bonds of bonds A and B.


Projecting away
from you, behind
H Projecting away from
plane of paper H you, behind H
109.5 plane of paper In plane
A of paper
1.09 A C C
H B C
H H H
D
H H H
H H
Tetrahedral structure
Projecting toward
you, in front of
plane of paper

Representations of the three-dimensional structure

Though tadious, it is the best method of representation.

2) Fischer projection :
Fischer projection is a standard way to project three diamensional configuration of
each carbon onto a plane surface. The projection looks like a cross with a chiral carbon at
the point where the lines cross.
The Fischer projection can be written in the following way:
If a molecule has a single chiral centre e.g.-D-glyceraldehyde, the carbon chain is drawn
vertical with the most oxidised atom at the top. Then mentally flatten the structure at each
chiral centre onto a plane surface.
The horizontal lines at the chiral center represent bonds that project forward.
The vertical lines at the chiral center actually represent bonds which project in the
rear.

CHO CHO
H OH H C OH
CH2OH CH2OH

Fischer formulae can be used for two or more chiral centres with,conventionally,
the longest carbon chain vertical, the bonds to top and bottom atom or groups go back, and
all the atoms or groups to one side or the other come forward.

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CHO CHO

H OH H C OH

HO H HO C H

H OH H C OH

H OH H C OH

CH2OH CH2OH

Fischer formula for the open chain form of D-glucose


Fischer projection formulae is convenient method for representing acyclic
compounds with one or more chiral centres.

3) Newman Projection :
Newmans projections are a way of drawing conformation.
To draw this formula we have to look along CC bond from the front.
The front carbon with its three substituents is denoted by inverted Y.
The back carbon is represented by a circle with three bonds pointing out from its periphery.

H Front carbon atom


H
H
H H H

C C
H
H H
H H
H Back carbon atom
Three-dimensional
Newman projection
projection formula
formula

4) Saw horse formula :


Sawhorse formula is the perspective formula which is used to specify a
conformation.
In sawhorse representation, the CC bond is viewed side ways due to which the
C C bond can be seen unlike in Newman projection.

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Newman projection Sawhorse projection


H
H H H H
H
H H
H H
H H
H
H H
H H H H
H H H
H
H
The eclipsed conformation The staggered conformation

CONFORMATIONS OF ETHANE

The two methyl groups in ethane are not fixed in a single positon. They are free to
rotate about the single bond connecting the two carbon atoms. The various structures
which result by rotation about a single bond are called as conformations.
H H

H C C H

H H

An infinite number of different conformations could result from rotations of the


CH3 groups about the carbon carbon sigma bond since the dihedral angle between the hydrogen
atoms on the front and back carbons can have an infinite number of values.
The two extreme conformations of ethane are
1)Staggered Conformation.
2)Eclipsed Conformation.
There are innumerable number of conformations in between these two extreme
forms called as skew conformations.

1)STAGGERED CONFORMATION
In the staggered conformation, dihedral angle ( ) i.e. the angle between C-H bonds
on the front carbon atom and the C-H bonds on the back carbon in the Newman projection,
is 60.

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= 60
H
H H

H H

H
Staggered

Stability :
The staggered conformation allows the maximum possible separation of the electron
pairs of the six carbon-hydrogen bonds thereby minimizing the repulsive interactions
between bonding pairs of electrons and therefore it has lowest energy.

2) Eclipsed Conformation :
The conformation of ethane with the dihedral angle of 0 is called eclipsed
conformation.
Newman projection of eclipsed conformation shows the hydrogen atoms on the
back carbon to be hidden (eclipsed ) by those on the front carbon.

= 0

H H H H

H
H
Eclipsed

Stability :
In the eclipsed conformation, the electron pairs of the six carbon-hydrogen bonds
are closest and therefore eclipsing leads to steric repulsion of hydrogen atoms that are not
directly bonded. These non bonded interactions raises the energy of eclipsed conformation by
about 3 kcal/mol. It is of highest energy and has the least stability.
3) Skew Conformation :
Any conformation of ethane that is not precisely staggered nor eclipsed is called as skew
Conformation.

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Stability :
In any Skew conformation of ethane, electron pairs of the cabon-hydrogen bonds
are not so far as in staggered conformation nor so close as in eclipsed conformation and
therefore it is more stable than eclipsed conformation and less stable than staggered
conformation.

TORSIONAL ENERGY
When ethane rotate towards eclipsed conformation, its potential energy increases which
leads to resistance to rotation. The resistance to twisting is called as torsional strain and 3 kcal/
mole energy needed is called torsional energy. The torsional energy of ethane in lowest in
staggered conformation. In the eclipsed conformation, the molecule is about 3 kcal/mol higher
in energy. This barrier is easily overcome at room temperature and the molecules rotate constantly.

CONFORMATIONS OF BUTANE
Focussing our attention on the middle CC bond in butane, we see a molecule
similar to ethane but with a methyl group replacing one hydrogen on each carbon.
H H

CH3 C C CH3

H H

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Due to the presence of the two methyl groups, two new point are encountered here
1) There are several staggered and eclipsed conformations.
2) van der Waals repulsion besides torsional strain plays important role in conformational
stabilities.

Various conformations of butane are discussed below :


1) ANTI CONFORMATION :
In anti conformation there is 180 dihedral angle between the largest groups.
In anti conformation of butane, the dihedral angle between two methyl groups is
180.

Stability :
The anti conformation does not have torsional strain because
a) the groups are staggered
b) two methyl grups are far apart from each other.
Therefore anti conformation is the most stable.

2) GAUCHE CONFORMATION
A conformation with a 600 dihedral angle between the largest groups is called
gauche conformation.
In the gauche conformation of butane, two methyl groups are 600 apart.

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Stability :
In the gauche conformation, the methyl groups are close enough to each other that the
van der Waals forces between them are repulsive.
This repulsion causes the gauche conformation to have approximately 3.8 kJ/mol energy
more than the anti conformation.

3) PARTLY ECLIPSED CONFORMATION :


Eclipsed conformation of butane in which dihedral angle between two methyl
groups is 1200 is known as partly eclipsed conformation.

Stability :
Partly eclipsed conformation has torsional strain. It also has additional van der Waals
repulsions arising from the eclipsed methyl groups and hydrogen atoms. These repulsions cause
partly eclipsed conformation to have energy 16 kJ/mol than the anti conformation.
4) FULLY ECLIPSED CONFORMATION
The conformation in which the methyl groups are pointed in the same direction
(dihedral angle = 00 ) is called fully eclipsed conformation.

Stability :
Fully eclipsed conformation has the greatest energy and thus least stability of all
because, in addition to torsional strain, there is added large van der Waals repulsive forces
between the eclipsed methyl groups.

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19 kJ mol-1
16 kJ mol-1 16 kJ mol -1
Potential energy

3.8 kJ mol-1 3.8 kJ mol-1

0 60 120 180 240 300 360

Rotation

CONFORMATIONS OF CYCLOHEXANE

Existance of an innumerable number of conformers in the case of cyclohexane as


happens in the case of ethane or butane is not possible. The number of conformers in the
case of cyclohexane are limited due to the presence of ring structure which is rigid.
Various conformations of cyclohexane are discussed below:

1) CHAIR CONFORMATION :
The chair conformation is free from angle strain since each angle is 1090 28.
In chair form all the C-H bonds are in staggered condition and thus it is free of
torsional strain. Thus the potential energy of chair form is minimum.

Chair (most stable)


2) BOAT CONFORMATION :
The Boat conformation is free from the angle strain since each angle is 1090 28'.
Two flagpole hydrogen atoms in the boat conformation lie only 1.83 A0 and thus
there is steric repulsion between them. Morover C2 and C6 are eclipsing C3 and C5 to which

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there is bond eclipsing strain.


The strain energy calculations indicate that the boat conformation is about 6.4 kcal/mol
higher in energy than the chair conformation.
4 H fp H fp
5 1
H (bs) H(bs)

3
Boat (Less stable)
3) Skew boat conformation :
When the two flagpole bonds in the boat conformation are moved apart, one gets a twist
or skew boat conformation.

Twist boat (Stable)


In the skew boat conformation, the flag pole hydrogens are thrown apart.
In the first conformer C2 and C5 and in the second twist form C3 and C6 have gone
down. Thus there is less strain in twist conformer than in the boat as there is less of hydrogen
eclipsing and flagpole interactions.
According to Hendrickson, the twist form contains 1.6 kcal/mol less energy than
the boat form.
The strain energy calculations indicate that the skew boat conformation is about
5 kcal/mol higher in energy than the chair conformation.
4) Half chair conformation :
A transition state conformer between the chair and twist forms is supposed to exist.
This is known as half chair conformer. This has a high strain. It has about 11 k cal/mole
energy than the chair form and is least stable.

Halt chair (List stable)


We can summarise the relative stabilities of the various conformations of
cyclohexane as :
chair > twist / skew boat > boat > half chair

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Half Chair Half Chair

10
Relative energy kJ mol-1

Boat
Twist Twist
45.2 kJ mol-1
5
30 kJ mol-1
23 kJ mol-1

Chair Chair

Chair Half Chair Twist Boat Twist Half Chair Chair

AXIAL AND EQUATORIAL BONDS IN CYCLOHEXANE


The bonds which are parallel to the three fold axis of symmetry of the chair are
known as axial bonds and those which extend outward from the ring are known as equatorial
bonds.

axial bonds Equatorial bonds


Each carbon atom of cyclohexane has one axial bond and one equatorial bond.

CONFORMATIONS OF MONOSUBSTITUTED CYCLOHEXANE DERIVATIVES


In the case of cyclohexane derivatives when one hydrogen atom is replaced by a
larger group or atom then the two chair forms are obtained in case of this mono substituted
derivative. The two isomeric chair forms difer in the position of substituent. In one isomer,
the substituent is axially located whereas in the other, the substituent is equatorially located.

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The stabilities of both the forms are different. Let us consider the case of methyl cyclohexane.
This molecule can have two isomeric chair forms whose stabilities would be different. The
two isomeric chair forms are
1) Axial isomer, 2) Equatorial isomer.
1) Axial Isomer :
In the axial conformer the methyl group is located at axial position. In this conformer,
the methyl group is so close to the two axial hydrogens on the same side of the molecule
(attached to C-3 and C-5 atoms) that the van der Waals forces between them are repulsive. This
type of steric strain, because it arises from an interaction between axial groups on carbon atoms
that have 1,3-relation, is called as a 1,3-diaxial interaction.

H
H
H 4 H
5 6 H
H
H
H 2 1
3 H H
H CH3
Axial

1,3diaxial methyl-hydrogen interaction is about 0.9 kcal/mole


The strain caused by a 1,3-diaxial interaction in methyl cyclohexane is the same as
the strain caused by the close proximity of the hydrogen atoms of methyl groups in the gauche
form of butane. These gauche interactions in the gauche butane causes gauche butane to be less
stable than anti-butane by 3.8 kJ/mol.

H
H
H H H
H C H
H C H
H C 4 3 2 H
H
H H
5 1
H H
H H H H
H 6
Axial methylcyclohexane
Gauche-Butane
(two gauche interactions =
(3.8 kJ mol -1 steric strain)
7.6 kJ mol -1 steric strain)

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2) Equatorial Isomer :
In the equatorial isomer, the methyl group is placed at equatorial position. In the equatorial
conformer the methyl group extends into space away from the rest of molecule because of which
its hydrogen atoms are far away It is free from diaxial interactions because equatorial methyl
group is anti to C-3 and C-5.

Equatorial
H H
H
H 5 6 1 CH 3
H
H 2
3 H
H 4 H
H
H

H H H

H 4 3 2 H

5 1
H
H C
H 6 H
H H

Equatorial methycyclohexane

STABILITY :
Equatorial conformer is more stable than axial conformer.

MAGNITUDE OF 1,3-DIAXIAL INTERACTION

The magnitude of the 1,3-axial interactions varies with different substituents. The
energy difference between the axial and equatorial conformers can be larger or smaller
depending on the substituent on the ring.

Conformational free energy :


The energy difference between conformers is known as conformational free energy
or A value. The important aspect of conformational analysis is that the two diastereomeric
chair forms are not of equal free energy and therefore are differently populated. In other
words we can say that the different monosubstitued cyclohexane derivatives display different
conformational preferances due to difference in energies of axial and equatorial conformers.

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CH3
CH3 C CH3
H H H
H
H H H
H H
H Ring flip H
CH3
H H
H H H
CH3 C H H
H H H
CH3 H

Equatorial tert-butylcyclohexane Axial tert-butylcyclohexane

There is a direct relationship between difference in energy, called the free energy
( G0 ) and the equilibrium constant (Keq) associated with a given equilibrium in solution
G0 = difference in free energy = RT l n keq
where R = gas constant ( 0.00199 kcal/mole)
T = absolute temperature at which the
equilibrium is measured.

The product of R, T and the natural logarithm of keq gives G0 i.e. the free energy
difference between the two conformers in kcal/mol.
G0 is usually negative is the difference of free energy between the equatorial and axial
conformer and G0 is known as conformational free energy of the substituent.
For substituted cyclohexane, it is conventional to specify the value of - G0 for the
equilibrium:
axial equatorial
G0 will be negative when the equitorial conformation is more stable than the axial. The
value of G0 is positive for the case of substituent groups which favour the equatorial position.

The larger the G0 , the greater is the preferance for the equatorial position.

Conformational free energies of substituent groups


Conformational free energy values for many substituent groups on cyclohexane ring are
determined by NMR spectroscopy. Conformational free energy values are measured at low
temperatures. It is believed that these values do not vary much at room temperature.

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Conformational free energies ( G) for Substituent Groups

Substituent G (kcal/mole)
F 0.24-0.28
Cl 0.53
Br 0.48
I 0.47
CH3 1.8
CH2 CH3 1.8
CH(CH3 )2 2.1
C(CH3 )3 >4.5
CH=CH2 1.7
C6 H5 2.9
CN 0.15-0.25
O2 CCH3 0.71
CO2H 1.35
CO2 C2 H5 1.1-1.2
OH (aprotic solvents) 0.52
OH (protic solvents) 0.87
OCH3 0.60
NO 2 1.16
HgBr 0

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Relationship Between Free-Energy Difference and Isomer Percentage for Isomers at


Equilibrium at 25C.

Free-Energy More Stable Isomer Less Stable Isomer


Difference, G (%) (%)
(kJ mol-1)
0 50 50
1.7 67 33
2.7 75 25
3.4 80 20
4.0 83 17
5.9 91 9
7.5 95 5
11 99 1
17 99.9 0.1
23 99.99 0.01

DISUBSTITUTED CYCLOHEXANE

The presence of two substituents on the ring of a cyclohexane allows for the
possibility of cis-trans isomerism. Geometrical isomerism in various disubstituted
cyclohexane is discussed below,
1,2- disubstituted cyclohexane :
The planar representation of the cis and trans isomers of 1,2- disubstituted cyclohexane
is as follows:-

H H CH 3 H

CH 3 CH3 H CH3

Cis -1,2-Dimethylcyclohexane Trans-1,2-Dimethylcyclohexane

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CIS FORM :
The cis isomer has two identical e,a- and a,e- conformations.
Consider cis-1,2- dimethyl cyclohexane, the two conformations are

CH3
H3C

H3C
CH3 CH3
CH3
eq,ax

cis conformation has three butane gauche interactions.

TRANS FORM :
There are two possible chair conformations of trans-1,2- disubstituted cyclohexane.
In one conformation, both the groups are axial; in the other both are equatorial.
The two chair conformations of 1,2- dimethyl cyclohexane are

CH3
CH3

CH3

ax, ax CH3

The diaxial form of trans-isomer in the case of 1,2- dimethyl cyclohexane has four
butane gauche interactions whereas the diequatorial form has only one, that between the
methyl groups. Thus, in the case of 1,2- dimethyl cyclohexane, the diequitorial trans isomer is
more stable than the cis isomer by about 1.8 kcal/mole.

1.3 - disubstituted cyclohexane


1,3- disubstituted cyclohexane exist in diastereomeric cis and trans forms whose
planar representation is as follows

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H CH3
H H
CH3 H
CH3 CH3

Cis-1,3-Dimethylcyclohexane Trans-1,3-Dimethylcyclohexane

CIS FORM :
There are two possible conformations of CIS form. In one conformation, both the
groups are axial whereas in the other, both are equatorial.
The two possible conformations of cis-1,3- dimethyl cyclohexane are given below.

CH3

CH3
CH3
ax, ax CH3

The diequatorial form of cis-1,3-dimethyl cyclohexane is more stable than the diaxial
conformation by about 5.4 kcal/mole. Thus diequatorial form is most preferred one.

TRANS FORM :
The trans isomer has two identical e,a and a, e conformations.
Consider trans-1,3- dimethyl cyclohexane with identical conformations.

CH3

CH3
CH3
CH3
ax, eq

The trans isomer of 1,3- dimethyl cyclohexane has two butane gauche interactions.
Thus the cis isomer is more stable by about 1.8 kcal/mole than the trans isomer.

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1.4 disubstituted cyclohexane :


The planar representation of the cis-trans isomers of 1,4- disubstituted cyclohexane
is as follows

H H H CH3

H3C CH3 H 3C H
Cis-1,4-Dimethylcyclohexane Trans-1,4-Dimethylcyclohexane

CIS FORM :
The cis isomer has two identical e,a and a,e conformation.
Consider the two identical conformations of cis-1,4- dimethyl cyclohexane.

CH3
CH3

CH3
ax, ax CH3

TRANS FORM :
There are two possible conformations of trans form of 1,4- disubstituted
cyclohexane,
In one conformation both the groups are axial; in other both are equatorial.
Consider the two conformations of trans-1,4- dimethyl cyclohexane.

CH3
CH3
H3C

ax, ax CH3

The diequatorial conformation is more stable than diaxial conformation and it represents
the structure of at least 99% of the molecules at equilibrium. The diaxial conformation has four
gauche interactions.

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Conformations and Energies of the Dimethylcyclohexanes

Isomer Conformation No. of gauche Interaction


interactions kcal./mole
e,a
cis-1,2 3 2.7
a,e
e,e 1 0.9
trans-1,2
a,a 4 3.6
a,a 4 5.4
cis-1,3
e,e 0 0
e,a
trans-1,3 2 1.8
a,e
e,a
cis-1,4 2 1.8
a,e
e,e 0 0
trans-1,4
a,a 4 3.6

PROBLEM :
a) Write structural formulas for the two chair conformations of cis-1-isopropyl-4-methyl
cyclohexane. b) Are these two conformations equivalent ? c) If not, which would be
more stable? d) Which would be the preferred conformation at equilibrium?
SOLUTION :

CH3
CH3
CH CH3

CH3 CH CH3
CH3

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PROBLEM :
a) Write the two conformations of cis-1,2-dimethylcyclohexane. b) Would these two
conformations have equal potential energy? c) What about the two conformations of
cis-1-terta-butyl-2-methylcyclohexane? d) Would the two conformations of trans-1,2-
dimethylcyclohexane have the same potential energy?
CH 3
H3 C

a) CH3
CH3

b) Yes
C(CH3)3
H3 C

CH3
C(CH3) 3
c)

H3C
CH3
CH 3
CH3
d)

CONFORMATIONAL EFFECTS ON STABILITY


The free energies of acyclic diastereoisomers usually differ. Generally meso forms are
more stable than d l pairs. This is illustrated by considering meso isomer and its active diastereo
isomer in their most stable conformations.

L L

S M M S

M S M
S
L L
Meso Active

Most stable conformation of meso and active isomers

L denotes the largest substituent, M the medium sized substituent, and S the small
substituent in the two isomers.
Chapter No. 7 : Concept of Chirality (Stereochemistry) 24
Notes for NET & SET - Chemical Sciences

The gauche interactions observed in the meso form are


2L-M+2L-S+2M-S+2L-M+2L-S.
The gauche interactions observed in the active form are
2M-S+2L-S+M-M+S-S.
The difference between the two forms is 2M-S-(M-M+S-S).
In general, the crossed steric interactions between two groups of unequal size are
less than the sum of interactions between the groups of like size i.e.(M-M+S-S)> 2M-S, provided
that interactions are purely steric in origin.
Thus it is follows from the above discussion that meso isomer is more stable than
the active isomer.

GEOMETRICAL ISOMERISM

Geometrical isomerism is another type of stereoisomerism arising out of different spatial


arrangement of groups attached to double bonds or rings in which stereoisomers are not readily
interconvertible.

GEOMETRICAL ISOMERS :
Geometrical isomers are stereoisomers which differ in spatial arrangement of atoms
or groups attached to double bonds or rings and this phenomenon is known as geometrical
isomerism.

CH 3 CH 3 CH 3 H

C C C C
H H H CH3

Geometrical isomers

H H Cl H

Cl Cl H Cl

Geometrical isomers

Chapter No. 7 : Concept of Chirality (Stereochemistry) 25


Notes for NET & SET - Chemical Sciences

RESTRICTED ROTATION AND THE DOUBLE BOND


Substituents attached to the C = C cant rotate freely since there is large energy
barrier to rotation associated with the groups joined by a double bond.

REASON FOR HINDERED ROTATION :


The C = C double bond consist of a bond and a bond; it is difficult to rotate
the substituents 1800 , since the bond must be broken, a reaction which requires about
264 kJ/mol of energy. Such a rotation will seldom happen at room temperature. The
inability of an olefinic double bond to rotate at room temperature is called hindered rotation.

GEOMETRIC ISOMERISM IN OLEFINS


There is hindered rotation about any carbon-carbon double bond but not all show
geometric isomerism. Geometric isomerism is only observed when there is a certain
relationship among the groups attached to the doubly bonded carbons.
The requirement for geometric isomerism is shown in following olefin.
Y A

C C
Z B
The requirement for geometric isomerism is A and B must be different groups, as
must Y and Z; However, either A or B can be same as Y or Z.
Thus, on this basis, we find that propylene, 1-butene and isobutylene do not show
isomerism.
H H H H H H
C C C No geometric
isomerism
C C C
CH 3 H Et H CH 3 CH3
Propylene 1-Butene Isobutylene

Geometric isomerism cant exist if either carbon carries two identical groups.

C
No isomerism
C
c d

Chapter No. 7 : Concept of Chirality (Stereochemistry) 26


Notes for NET & SET - Chemical Sciences

CIS-TRANS ISOMERS
The prefixes cis and trans work well to specify the geometric isomers.
CIS ISOMER :
The geometric isomer in which similar groups are present on the same side of the
double bond is refererd as cis isomer.
Cl H
C
Cis-1,2-dichloroethene
C
Cl H
TRANS ISOMER :
The geometric isomer in which similar groups are present on the opposite side of
the double bond is referred as trans isomer.
Cl H
C
trans-1,2-dichloroethene
C
H Cl
DRAWBACKS OF CIS-TRANS NOMENCLATURE
Cis-trans nomenclature fails to specify the configurations of following compounds.
H3 C H H3 C H H Cl H Cl
C C C C

C C C C
Br Cl Cl Br Cl Br Br Cl

E-Z SYSTEM OF NOMENCLATURE

E-Z system of nomenclature for geometric isomers have been developed after Cahn-
Ingold-Prelog convention for chiral carbon atoms.
In order to assign E-Z nomenclature to geometric isomer :
1) The two groups attached to each carbon of the double bond are arranged in order of
priority.
2) If the two groups of highest priority are together on the same side of the double bond
then the configuration is called as the Z isomer.
3) If the two groups of highest priority are on the opposite sides of the double bond then the
configuration is called as the E isomer.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 27


Notes for NET & SET - Chemical Sciences

1 Together 1 1 Opposite
2
Br Z CH3 Cl CH 3 E
C C C C
2 Cl H 2 1 Br H 2

(Z)-1-bromo-1-chloropropene (E)-1-bromo-1-chloropropene

H3 C CH3 H 3C H
CH 3 > H
C C CH 3 > H C C
H H H CH3
(Z)-2-Butene (E)-2-Butene

Br Cl
CH3 > F
C C
CH3 > H F
H
Z

Br CH 3 Cl CH 3 CH 3 CH2CH 2CH3
C C C C C C
Cl H Br H H CH 2CH 3
(I) (II) (III)

When an alkene has more than one double bond, the stereochemistry about each
double bond can be specified with E and Z nomenclature.

1
Br 1

1
3-bromo-(3Z,5E)-octadiene

The E-Z nomenclature can also be used to designate cyclic compounds. When the two
higher priority groups are on the same side of the ring then the compound is called as Z isomer
and when these groups are on opposite sides of the ring, the compound is called as E isomer.

H H H CH 3

CH3 CH 3 CH 3 H
Z-1,2-dimethylcyclopropane E-1,2-dimethylcyclopropane

Chapter No. 7 : Concept of Chirality (Stereochemistry) 28


Notes for NET & SET - Chemical Sciences

The Z or E isomers are not necessarily always the ones which would be called cis
or trans isomers respectively under the old nomenclature because E and Z nomenclature
depends on the priorities of the groups attached to the unsaturated carbon atoms.

Cl Cl Cl Br
Cl >H
C C C C
Br > Cl
H Br H Cl
(E)-1-Bromo-1,2-dichloroethene (Z)-1-Bromo-1,2-dichloroethene
(cis-1-bromo-1,2-dichloroethene) (trans-1-bromo-1,2-dichloroethene)

OLEFINS AND CHIRALITY


The compounds which show cis-trans isomerism with one double bond are not
chiral because the four groups are in one plane.
When the compound contains odd number of cumulative double bond
(three,five,etc) then orbital overlap causes the four groups to occupy one plane and hence
cis-trans isomerism is observed in such compounds.
When the compound contains even number of cumulative double bonds and when
the both sides are disymmetric then optical activity is possible in such compounds.

MULTIPLE DOUBLE BONDS :


If a molecule has more than one double bond, each substituted properly so as to
give geometrical isomerism, then the number of possible geometric isomers of it will be
2n . Thus four geometric isomers should exist if there are two such double bonds. The four
isomers of 5-cyclohexyl-2,4-pentadien-1-0l are shown below; these are designated as
trans-trans,cis-cis-,trans-cis,and cis-trans.

H H
H C C
CH2OH
C C H C C
H C C H H
H CH2OH
Trans-trans Cis-cis

Chapter No. 7 : Concept of Chirality (Stereochemistry) 29


Notes for NET & SET - Chemical Sciences

H CH2OH
H C C
H
C C CH2OH C C
H C C H H
H H
Trans-cis Cis-trans

Geometric isomers of 5-cyclohexyl-2,4-pentadien-1-0 l


Vitamin A has five double bonds thus the total number of possible isomers is 25 =32.

PROPERTIES OF GEOMETRICAL ISOMERS


A pair of geometric isomers can be referred as diastereomers. Thus as far as chemical
and physical properties are concerned, geometric isomers show the same relationship to
each other as do the other diastereomers.
Chemical Properties :
The chemical properties of geometrical isomers are not identical, however, since their
structures are neither identical nor mirror images; they react with the same reagents, but at different
rates.(Under certain conditions-especially in biological systems-geometrical isomers can very
widely in their chemical behaviour).
Physical Properties :
Geometrical isomers have different physical properties such as melting points,
boiling points, refractive indices, solubilities, densities etc.
They can be distinguished from each other on the basis of their physical properties.
On the basis of the differences in physical properties they can be separated.

INTERCONVRSION OF GEOMETRICAL ISOMERS


The most straight forward way of interconverting geometrical isomers is by heating.
The cis and trans isomers can be interconverted at higher temperatures or by irradiation
with light of suitable wavelength.
The interconversion of isomers involves the breaking of the bond of the carbon-
carbon double bond followed by rotation about the carbon-carbon bond and subsequent
reformation of a new bond.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 30


Notes for NET & SET - Chemical Sciences

OPTICAL ISOMERISM

ORDINARY AND PLANE POLARIZED LIGHT


The nature of light is such that no purely verbal description can adeqately represent
all of its properties. However one of the oldest and most successful attempts at a description
of this phenomenon treats light as a form of energy which is transmitted in waves.
When an ordinary light is passed through a Nicol prism, it is converted into plane polarized
light. Plane polarized light can be defined as the light whose waves vibrate in one direction
(plane).
When ordinary light from a source with an infinite number of planes is passed through a
Nicol prism, only a single plane is allowed to emerge.

Ordinary light Plane polarized light

OPTICAL ACTIVITY
Certain substances have ability to rotate the plane of polarized light
are called as optically active compounds and this phenomenon of rotating the plane of
polarized light is called optically activity.
If the substance does not rotate the plane of polarized light, it is considered to be optically
inactive.
DEXTRO AND LAEVO ROTATORY SUBSTANCES
Optically active compound may rotate the plane of polarized light to the right or to the
left.
The substances which rotate the plane of plane polarized light to the right are called as
dextrorotatory and are designated as d or (+).
The substances which rotate the plane of plane polarized light to the
left are called as laevorotatory and are designated as l ().

SPECIFIC ROTATION
The presence of optical activity, its direction and extent of rotation is measured by
an instrument called polarimeter.
Chapter No. 7 : Concept of Chirality (Stereochemistry) 31
Notes for NET & SET - Chemical Sciences

The optical activity of a compound is reported as its specific rotation.


OPTICAL ROTATION :
If polarized light is allowed to pass through a solution of an optically active compound
then the single plane of polarized light will be rotated. The rotated light is then allowed to
pass through a second prism. This prism is rotated until the plane of light is again vertical.
The angle that the second prism must be moved to bring the light back to vertical is called as
optical rotation( ).

Diagram : Rotation of a plane of polarized light by an optically active organic molecule.


The dotted line indicates the original plane of light and the degree of rotation from
original plane.
Optical rotation is a function of concentration,sample thickness,
temperature,wavelength of polarised light etc.

SPECIFIC ROTATION:-[ ] : Specific rotation is the number of degrees of rotation of


the plane polarized light to the wavelength of the sodium D line (5890 A0 ) when passed through
a solution of concentration 1gm/ml in a 1-decimeter tube.
Optical rotation is usually recorded in terms of specific rotation.
The equation to determine specific rotation [ ] is

=
C. l
Where [ ]=specific rotation.
= observed rotation.
C = the concentration of the solution in gms/ml of solution.
l = the length of the tube in decimeters (1dm=10cm).
The specific rotation depends on the temperature and the wavelength of light that
is employed and hence specific rotations are reported so as to incorporate these quantities.
A specific rotation might be given as follows:

25 = +312
.
0

Chapter No. 7 : Concept of Chirality (Stereochemistry) 32


Notes for NET & SET - Chemical Sciences

This means that the D line of a sodium lamp was used for the light, that a temperature of
250 C was maintained and that a sample containing 1.00g/ml of the optically active substance, in
a 1 dm tube, produced a rotation of 3.120 in a clockwise direction.
The specific rotation is considered as another physical constant like melting point,
boiling point, or density.

PROBLEMS ON SPECIFIC ROTATION


1) The concentration of cholesterol dissolved in CHCl3 is 6.15 gms per 100 ml. of solution.
A) A portion of this solution in a 5 cm polarimeter tube causes an observed rotation of -
1.20 . Calculate the specific rotation of cholesterol.
B) Predict the observed rotation if the same solution were placed in a 10 cm. tube.
Solution :
A] -390
B] -2.4
2) An aqueous solution of pure compound of concentration 0.10 g/ml had observed
rotation -300 in a 1.0-dm tube at 589.6 nm and 250 C. Determine the specific rotation.
Solution : -3000

CAUSE OF OPTICAL ACTIVITY


1] The theory of Vant Hoff and Le Bel:-
By 1874,over a dozen examples of optically active organic molecules were known.
In every case at least one carbon in the molecule had four different groups attached to it.
Vant Haff and Le Bel related the phenomenon of optical rotaton to the presence of
asymmetrically substituted carbon atoms (chiral carbon atoms) in the molecules.
Chiral Carbon:-
If the carbon atom is attached to four different groups or atoms, it is called chiral
carbon.
COOH
*
CH3 C OH Asymmetric carbon atom
H
In the case of organic compounds, the presence of chiral carbon is most probable cause
of optical activity.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 33


Notes for NET & SET - Chemical Sciences

They also realised that there could exist optically active compounds having no asymmetric
atoms.
They also observed that many compounds were optically inactive though they contained
two or more asymmetric carbon atoms.
COOH
CH3
Cl *
H C OH
C C C *
H C OH
H
CMe3
COOH

Optically active though Optically inactive though contains


doesnt contains asymmetric two asymmetric carbon atoms
carbon atoms

Thus the concept of asymmetric carbon atoms could not explain satisfactorily the cause of
optical activity.
The theory of Vant Hoff and Le Bel States that,for a molecule or a crystal to be
optically active,its mirror image must be non superimposable. Whereas a molecule with
superimposable mirror image is optically inactive.

NON SUPERIMPOSABLE MIRROR IMAGE


An object or molecule or crystal can be superimposable on its mirror image when
it has any one of the following elements of symmetry :
1)Plane of Symmetry
2)Centre of Symmetry
3)Alternating axis of Symmetry

1) Plane of Symmetry :
A molecule is said to possess as plane of symmetry when an imaginary plane passing
through the centre of molecule can divide it into two parts such that one is the exact mirror image
of the other.
If a molecule has plane of symmetry then the molecule and its mirror image are
superimposable and hence molecule is optically inactive or achiral.
Few molecules with plane of symmetry are shown below :

Chapter No. 7 : Concept of Chirality (Stereochemistry) 34


Notes for NET & SET - Chemical Sciences

OH

HO C COOH

HO C COOH Plane of symmetry

OH

Plane of symmetry

H H

CH3 CH3

CH3 CH3
H H

CH3 CH3 H H

CH3

H H

Br Br
CH3

2) Centre of Symmetry :
It is an imaginary point in the molecule from which the similar groups are at
equidistant.
Generally centre of symmetry is observed in the even membered rings.
The compounds having centre of symmetry are optically inactive or achiral.
Following isomer of 1,3-dichloro -2,4- difluoro cyclo butane has a centre of Symmetry:

Chapter No. 7 : Concept of Chirality (Stereochemistry) 35


Notes for NET & SET - Chemical Sciences

Cl H

F H H F

H Cl

3) Alternating axis of Symmetry :-


It is a line about which the crystal may be rotated so that it represents the same appearance
more than once during a complete revolution.

H3 C
C2 H5
tin g
r ota C
f te r
A 1 8 0
ro u gh
Th
Br Br Br

(b)
C
H3 C H 3C C
C2 H 5
C 2H 5
Plane of
H3C
Br mirror
C2 H5
C

Br C
H 2C
(a) C 2H5
Line passing through
centre of molecule H3 C
C2 H5
C
(c)
Br Mirror image of b
(identical with a)
Alternating axis of symmetry
Many compounds which posses alternating axis of symmetry are achiral.

A molecule is said to have alternating axis symmetry,if an identical structure results when
it is rotated around the axis by an angle of 2 /n (n=number of fold of Symmetry) and then
reflected across the plane perpendicular to the axis. For example, 3, 4-dibromo-3, 4-dimethyl
hexane has alternating axis of symmetry.
Many compounds which possess alternating axis of symmetry are achiral.
Thus a molecule that has a plane of symmetry,a center of symmetry and an alternating
axis of symmetry is superimposable on its mirror image and is optically inactive and a

Chapter No. 7 : Concept of Chirality (Stereochemistry) 36


Notes for NET & SET - Chemical Sciences

molecule that has no element of symmetry is not superimposable with its mirror image and is
optically active.

CONDITION OF OPTICAL ACTIVITY


A chiral molecule has a center of chirality within it and it consist of a suitable atom
substituted in a way so as to be non superimposable on its mirror image. Thus chirality is
the property of a molecule of being non superimposable on its mirror image. The most
common feature which gives chirality to the molecule is a chiral centre but not always.
We can say that many but not all molecules that contain chiral centre are chiral and many
but not all chiral molecules contain chiral centre.
Chirality is necessary and sufficient condition for exhibiting optical activity.
The optical activity of sodium bromate, sodium iodate, quartz is lost when their
lattice structure is destroyed by melting or dissolving in water. This indicates that chirality
is in the lattice structure.
Many organic compounds show optical activity even in solid, liquid, vapour or in
solution form. This indicates that chirality is inherent in the molecule. Hence, they show
optical activity even if their physical state is changed. That is they have molecular chirality.

ASYMMETRIC AND DISSYMMETRIC MOLECULES


A disymmetric molecule lacks those elements of symmetry which preclude a mirror
image relationship, whereas asymmetric molecule has no elements of symmetry at all.
Disymmetric and asymmetric molecules are usually optically active.
(A molecule having none of the elements of symmetry which preclude a mirror image
relationship or having only an axis of symmetry is not superimposable with its mirror
image and is called disymmetric.)

DETERMINING WHETHER A MOLECULE IS CHIRAL OR NOT


A foolproof method to determine whether a molecule is chiral or not, is to construct
molecular models of the molecule and its mirror image relationship and look if these pass
the test of superimposition. The chiral molecules are those in which object is non super
imposable on its mirror image.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 37


Notes for NET & SET - Chemical Sciences

H H

Achiral or Meso compound because contains plane of symmetry

Cl Cl

Cl Cl

Achiral because contains plane of symmetry

H Cl

Chiral because has non superimposible mirror image

Cl H

CH3

H H
Achiral because has plane of symmetry.
CH 3

H H

Achiral because has plane of symmetry


CH 3 CH3

H Cl
Chiral because has non superimposible mirror image
Cl H

Cl Cl

Chiral because has non superimposable mirror image


Cl H

Chapter No. 7 : Concept of Chirality (Stereochemistry) 38


Notes for NET & SET - Chemical Sciences

Achiral (Plane of symmetry)


CH 3 CH3

Chiral
CH 3 Cl

Chiral
CH 3 CH3

Chiral
CH 3 Cl

CH 3

Achiral (Plane of symmetry)

CH3

CH3

Chiral

CH3

Chapter No. 7 : Concept of Chirality (Stereochemistry) 39


Notes for NET & SET - Chemical Sciences

CH 3

Chiral

C2 H5

CH 3

Chiral

C2 H5

CH 3

Achiral

CH 3

CH 3

Achiral

C2 H5

CHIRAL COMPOUND WITHOUT CHIRAL CENTRE


The presence or absence of chiral centre is no criteria for chirality. Many compounds
are chiral though they do not contain chiral centre. Some of such compounds are listed below :
1) BIPHENYLS :
Properly substituted biphenyls are chiral. Their chirality is due to restricted rotation
about the central bond (atropisomerism). Biphenyls with heavy groups in the ortho positions
when substituted suitably cant rotate freely about the central bond because of steric
hinerance. In biphenyls, two rings are in perpendicular planes. Biphenyls are chiral provided
both sides are dissymmetric. Introduction of bulky o-substitutents would prevent free rotation of
Chapter No. 7 : Concept of Chirality (Stereochemistry) 40
Notes for NET & SET - Chemical Sciences

the nuclei about the coaxis and at the same time produce a coaxial twist. Hence the two benzene
rings cannot be coplanar due to impingement of the o-substituents and thus biphenyls become
dissymmetric.

NO2
HOOC

NO2
COOH

2) ALLENES :
Suitably substituted allenes are chiral provided both the sides are dissymmetric.
Following types of allenes will be dissymmetric provided that a b.
a a
a a
C C C C C C
b b
b b

Enantiomeric allenes
Molecular dissymmetry is possible because the groups at one end of the allene
molecule lie in a plane at right angles to those at the other end.
(c)
(a)
C C C
(b)
(d)

3) SPIRANES :
Suitably substituted spiranes are chiral provided both sides are dissymmetric.
In spiranes, the two rings are orthogonal as a consequence,groups attached to the
ends of the system lie in planes which are mutually perpendicular.
Dissymmetric spiranes are obtained by attaching unequal substituents at each end
of the system.

H H
H R
R R

dissymetric spiranes

Chapter No. 7 : Concept of Chirality (Stereochemistry) 41


Notes for NET & SET - Chemical Sciences

(a)
(c)

(b) (d)

4) METHYLENE CYCLOALKANES :
Substituted methylene cycloalkanes are chiral provided both sides are dissymmetric.
4-Methyl cyclohexyliden acetic acid was the first chiral compound of this type that
was reported.
H COOH
C
H
CH 3

4-Methyl cyclohexyliden acetic acid


This substituted methylenecyclohexane is dissymmetric because the groups attached to
the double bond lie in a plane at right angle to those attached to the 4-position of ring.
Another example of dissymmetric methylene cyclohexane is show below:-
H H (a) (c)
C

CH 3 CH3 (b) (d)

Chapter No. 7 : Concept of Chirality (Stereochemistry) 42


Notes for NET & SET - Chemical Sciences

OPTICAL ISOMERS

The stereoisomers which are otherwise same but differ in their action towards the
plane polarised light are called optical isomers and this phenomenon is called optical
isomerism.
Eg:- d-lactic acid and l - Lactic acid are optical isomers.
COOH COOH

C C
H OH OH H

CH3 CH3

d-lactic acid l - lactic acid


[ ] = +2.24 [ ] = 2.24
Similarly d-tartaric acid and l -tartaric acid are optical isomers.

ENANTIOMERS
Stereoisomers that are mirror images of each other are called as enantiomers.
Eg:- d-lactic and l -lactic acid are enantiomers.

COOH COOH

C C
H OH OH H
CH3 CH3

d-lactic acid l - lactic acid

PROPERTIES OF ENANTIOMERS
1)Enantiomers have identical physical properties such as boiling point, refractive index,
relative density etc but differ each other in their action on plane polarized light. If one of
the enantiomer rotate the plane of plane polarized light to the right, the other will rotate to
the left. However the extent of rotation is same.
Eg- The properties of two 2-methyl-1-butanols are shown below :

Chapter No. 7 : Concept of Chirality (Stereochemistry) 43


Notes for NET & SET - Chemical Sciences

Property (+)-2-Methyl-1-butanol ()-2-Methyl-1-butanol


Specific rotation +5.90 5.90
Boiling point 128.9C 128.9C
Relative density 0.8193 0.8193
Refractive index 1.4107 1.4107
2) Enantiomers have same chemical properties except the fact that they differ in the rate of
reaction with the other optically active reagents (chiral probes).
DIASTEREOISOMERS
Stereoisomers that are not mirror images of each other are called diastereoisomers.
e.g. :

CH3 CH 3

H Br H Br

H Cl Cl H

CH3 CH 3
(I) (II)

(I) and (II) are diastereomers.


PROPERTIES OF DIASTEREOMERS
1)Diastereoisomers have different physical properties :
Diastereomers have different physical properties like melting points,boiling
points,solubilities in a given solvent,densities,refractive indexes etc. Diastereomers differ
in specific rotaton;they may have the same or opposite signs of rotation, or some may be
inactive.
2)Diastereoisomers have different chemical properties.

EPIMERS AND ANOMERS

Several sugars are closely related to each other and differ only by the stereochemistry
at a single carbon atom. Sugars which differ only by the stereochemistry at a single carbon
atom are called epimers. The carbon atom where the two sugars differ is generally stated
and when it is not stated it is assumed to be C-2.
Eg- D(+)- glucose and D(+) mannose are C-2 epimers.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 44


Notes for NET & SET - Chemical Sciences

CHO CHO

H OH OH H

HO H HO H

H OH H OH

H OH H OH

CH 2OH CH2 OH

D (+) - glucose D (+) mannose


C2 Epimers
Similarly D-glucose and D-Galactose are C-4 epimers.

CHO CHO

H OH H OH

HO H HO H

OH H H OH

H OH H OH

CH 2OH CH2 OH

C-4 Epimers
Anomers :
Glucose and other hexoses exist as an equilibrium mixture with their cyclic
hemiacetal isomers in which the latter strongly predominates. The carbonyl carbon turns
into a new stereocenter on cylcization. Thus glucose has two cyclic forms which differ
only in the stereochemistry at C-1 and the hemiacetal carbon is called as the anomeric
carbon. Such isomers are called as anomers. The two anomers are commonly differentiated
by the Greek letters and and thus in the case of glucose these diastereomers are
termed -D-glucose and -D- glucose.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 45


Notes for NET & SET - Chemical Sciences

HO H H HO

H OH H OH

OH H OH H

H OH H OH

H H
CH 2OH CH 2OH

-D-Glucose -D-Glucose
Anomers

STUDY AID

An approach to the classification of Isomers :


We can classify isomers by asking and answering a series of a questions :

Do the Molecules
have the same Not isomers
molecular formula ?
Yes
Yes
Are they superimposable ? Homomers

Isomers

Do they have the same Structural isomers


molecular constitution ?
Yes

Stereomers

Are they non-superimposable


mirror images ?

Yes

Enantiomers Diasteromers

Chapter No. 7 : Concept of Chirality (Stereochemistry) 46


Notes for NET & SET - Chemical Sciences

SOME SOLVED PROBLEMS


1) Find out the enantiomeric pair amongst following compounds.

COOH COOH COOH

H OH H OH HO H

H OH HO H H OH

COOH COOH COOH


(A) (B) (C)

Solution : B and C are enantiomeric pair.


2) Find out relationship between i and ii.

CH 3 CH3

H OH H OH

H OH HO H

H OH H OH

CH 3 CH3
( i) ( ii )

Solution : i and ii are diastereomers.


3) Choose the correct relation of (ii) and (iii) with (i).

CH 3 CH3 CH3

CH3 CH3 CH 3
( i) ( ii ) ( iii )

Solution : Compound (ii) is a diastereomer of (i) whereas (iii) is enantiomer of (i).

Chapter No. 7 : Concept of Chirality (Stereochemistry) 47


Notes for NET & SET - Chemical Sciences

4) Identify the relationship between following pairs of structures.

Cl Cl

And
a)
Cl Cl

CH 3 CH 3

H Cl Cl H
And
b) H Br Br H

CH 3 CH 3

Cl Cl Cl
Cl

And
c)
Cl Cl Cl Cl

d) And

CH 3 CH 3

H Cl Cl H
And
e) H Cl H Cl

CH 3 CH 3

Solution :
a) Diastereomers
b) Enantiomers
c) Same
d) Constitutional isomers
e) Diastereomers

Chapter No. 7 : Concept of Chirality (Stereochemistry) 48


Notes for NET & SET - Chemical Sciences

DETERMINING NUMBER OF STEREOISOMERS


According to vant Hoffs rule, the maximum number of optical isomers for a molecule
having plural centres of asymmetry is 2n , where n is the number of asymmetric carbons.
Eg- D-Glucose whose structure can be abbreviated as HOCH2 (CHOH)4 CHO
has four asymmetric carbon atoms and therefore there are 24 or 16 isomers of this structure.
One of these is D-Glucose and one of the remaining 15 is its mirror image,L-glucose and
remaining 14 isomers of D-Glucose are diastereomers.

SOLVED EXAMPLES
1)How many stereoisomers are possible for cholesterol.

OH H
H3C

H H

OH

Solution : Number of stereoisomers =28 =256.

2)Menthol has three asymmetric centres. How many epimers and diastereoisomers
are possible for it?
Solution : 3 Epimers and 6 diastereoisomers.

3)Methyl-D-glusoside has five asymmetric centres how many epimers(E) and


diastereoisomer(D) are possible for this molecule?
HO

O O Me
HO

HO

Solution : 5 Epimers and 30 Diastereoisomers.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 49


Notes for NET & SET - Chemical Sciences

4)Natural cholesterol on hydrogenation affords cholestanol as one of the products

H H

HO
H

Cholestanol
As this compound has nine asymmetric centres, it can exists as 29 i.e. 512 possible
isomers. The number of diastereomers of cholestanol are
Solution : 510.

RACEMIC MIXTURE

Racemic modification or mixture is defined as a mixture containing equimolar


quantities of a pair of enantiomers. It is represented as, () or dl.
When a pair of enantiomers is mixed in equal molar proportion, the resulting mixture
do not show optical activity and it is called racemic mixture.
The optical inactivity is because, the right hand rotation (+) by dextro component
is nullified by equal left hand rotation () by laevo component, since they are present in
equal proportion. This type of compensation is called external compensation.

RESOLUTION
The separation of enantiomers from a racemic mixture is called as resolution. Since
enantiomers have almost similar physical and chemical properties, it is difficult to separate
them from racemic mixture.

METHODS OF RESOLUTION
Various methods of resolution are discussed below.
1) USING CHIRAL PROBE :
Resolution is carried out by converting the mixture of enantiomers (recemic mixture)
into a mixture of diastereomers by using chiral compound called as resolving agent. Since

Chapter No. 7 : Concept of Chirality (Stereochemistry) 50


Notes for NET & SET - Chemical Sciences

the resulting products will be diastereomeric, these can be separated. Separated diastereomers
are converted back to enantiomers.

CO 2H This is the
resolving agent
H C OH

CH 3
NH2
+NH CO2
( R ) - lactic acid 3

+ C6 H5 C CH 3 C 6H 5 C CH3 H C OH
CO 2H H H CH3
HO C H ( S )-1-phenylethylamine ( S )-1-phenylethylammonium ( R ) - lactate

CH 3
+NH CO2
( S ) - lactic acid 3
C 6H 5 C CH3 HO C H
Racemic ( R,S )-acid
H CH3
( S )-1-phenylethylammonium ( S ) - lactate

These salts are diastereomers


and can be separated

a) Resolution of Acids and Bases :


Acid-base reactions are often used to resolve racemic acids and bases.
A racemic acid reacts with optically active base to form diastereomeric salts which
can be separated. Separated diastereomeric salts are then converted back into enantiomers.

( S )- acid (S,S)- salt


+ (S)- amine + Separate
(S,S)- salt + (S,R)- salt
( R )- acid (S,R)- salt HCl HCl

( S )- acid ( R )- acid
+ +
( S )-ammonium ( S )-ammonium
chloride chloride

The resolution of the racemic form of an organic acid


Similaraly, a racemic base reacts with optically active acid to form diastereomeric salts
which can be separated. Separated diastereomeric salts are then converted back into enantiomers
by conventional methods.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 51


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b) Resolution of other compounds :


Racemic compounds which are neither acids nor bases are often resolved by first attaching
an acidic handle. Consider an example of racemic alcohol. A racemic alcohol reacts with cyclic
anhydride to form both an ester and an acid. The racemic acid thus produced is separated via
diastereomeric salts and converted back to the enantiomeric acids. The acidic handle is then
removed by hydrolysis of the ester group and the separated alcohol enantiomers are obtained.

O
O
C
(+)RCH 2OH CH2 (+)R CH2 OC CH2CH 2 CO2 H
O
+ O
CH2
(-)RCH2 OH (-)R CH 2OC CH 2CH2 CO 2H
C

Racemic Succinic Racemic acid


alocohol anhydride

(+) R- CH2OCCH2 CH 2COH (+) R- CH2 OH

Various naturally occuring alkaloids (optically active) are available for the resolution
of racemic acids. Common examples are strychnine, brucine, morphine, ephedrine,
cinchonine, quinine, quinidine. One of the most important synthetic basic resolving agent
is -phenyl ethyl amine. Among the acids which are used in the resolution of racemic
bases are camphoric acid, camphor-10-sulphonic acid, methyoxy acetic acid and pyrrolidine-
5-carboxylic acid

2) CHROMATOGRAPHIC TECHNIQUES
The resolution by using chromatography depends on the difference in the rates of
reaction of the two enantiomers with the chiral probe material on the column packing.
The method involves preparation of column of solid optically active compounds
like tartaric acid, sucrose etc. The enantiomeric components of the racemic mixture form

Chapter No. 7 : Concept of Chirality (Stereochemistry) 52


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diastereomeric complexes with the chiral material used on column. (one enantiomer passes through
the chromatographic column faster than the other due to varied rate with the chiral material).
The racemic mandelic acid has been resolved by column chromatography on starch.
Racemic p- phenylenebisiminocamphor has been resolved on lactose column.
Racemic Trogers base has been resolved on lactose column.

3) ENZYMATIC RESOLUTION
Enzymes are complex optically active protenoid catalysts which are produced by
living organism. A fundamental property of enzymatic reactions is high degree of
stereoselectivity due to the asymmetric nature of enzymes. Enzymes show different rates
of reaction with the two enantiomers. For example, a certain bacterium digest only one
enantiomer and not the other. This method has limiting value since one of the enantiomer
is destroyed during resolution.
E.g. : Penicillium glaucum destroys ammonium (+) tartarate more rapidly than the (-)
tartarate in a dilute solution of ammonium () tartartes.
Racemic -amino acids are resolved by using swine kidney acylase.

4) MECHANICAL SEPARATION
Enantiomers of very few substances can be crystallised into asymmetric crystals.
Since the appearance of these crystals are different, a trained crystallographer can
separate them with tweezers.
The method was first time used by Pasteur. The mechanical separation is an attractive
method for effective resolution. However, difficulties arise due to the fact that very few
substances can be crystallised into asymmetric crystals. Sodium ammonium tartarate is
one of this rare group of compounds, and even in this case the crystalization must be
carried out below 270 C.

5) DIFFERENTIAL REACTIVITY
Since enantiomers react with chiral compounds at different rates, it may be possible
to effect a partial separation by stopping the reaction before it goes to completion.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 53


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R & S NOMENCLATURE

The R, S convention is governed by three rules which are quite logical and easy to
remember; these rules set a priority sequence for the four substituents, A, B, D, E, about an
asymmetric carbon.

Rule-1 : The priorities assigned to the four substituents on an asymmetric carbon depend
upon the atomic number of the attached atom. Greater the atomic number of atom, greater
is the priority. [For example, the halogens have the priority I > Br > Cl > F ; other obvious
priorities would be Cl > O > N > C.]
Let us now consider the configurational assignment for bromochlorofluoromethane,
which has the atomic priorities Br > Cl > F > H. Visualize the molecule in such a way that
the atom with lowest priority projects behind the paper ; the remaining three substituents
are arranged in order of priority either clockwise or counterclockwise as follows

Cl Cl

C C H
H
Br F F Br

Clockwise Counterclockwise
(R) configuration (S) configuration

The clockwise direction is assigned the R configuration (Latin: rectus, right) and
the counterclockwise direction is assigned the S configuration (Latin: sinister, left).

Rule2 : When two or more substiuents on the asymmetric carbon have atoms with the
same atomic number, then Rule 2 applies; precedence is given to the substituent with the
highest atomic number in the second atom from the asymmetric center.
For example, with sec-butyl alcohol, two of the adjacent atoms are C. However,
the C of -CH2 -CH3 is bonded to C, whereas the C of -CH3 is bonded only to H; therefore,
-CH2 -CH3 takes priority order for sec-buty1 alcohol is OH > C2 H5 > CH3 > H.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 54


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OH

CH 3CH 2 C CH3

H
sec-Butyl alcohol
Rule3 : If the second atom from the asymmetric center has an identical atomic number in two
groups, then the total of the atomic numbers attached to the first carbon are considered. With this
O
rule a double bond, -C=A, is treated as -CA2 ; for example, -C=O would be treated as C .
O
Similarly a triple bond, C A, would be treated as -CA3 .
With this rule, the carboxy1 (-COOH) with combined atomic numbers of 48 would
take precedence over an aldehyde (-CH=O) with combined atomic numbers of 33; similarly
-CH=O would take precedence over -CH2 OH (combined atomic numbers = 18). Thus in
the case of glyceraldehyde, the priorities are
OH > -CH=O > CH2 OH > H.
The phenyl substituent is treated as -C-C3 with combined atomic numbers of 36; thus
phenyl would take priority over isopropy1, -CH(CH3 )2 , with combined atomic numbers of 25.
By applying these rules to some common substituents, one obtains the following sequence
(group of highest priority first): I, Br, Cl, SO2 R, SOR, SR, SH, F, OCOR, OR, OH, NO2 ,
NHCOR, NR2 , NHR, NH2 , CCI3 , COCI, CO2 R, CONH2 , COR, CHO, CR2 OH, CHOHR,
CH2 OH, CR3 , C6 H5 , CHR2 , CH2 R, CH3 , D, H.

CHO

C
H
HO CH2OH
R-Glyceraldehyde

COOH

C
H
H3C NH2
S - Alanine

If more than one asymmetric carbon is present, then each configuration is specified,
along with the position number of the asymmetric carbon.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 55


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H
HO COOH
C

C
HOOC OH
H

2(R), (R)-Tartaric acid

CHO
CO 2H
HO C H
H C OH
H C OH
HO C H
H C OH
CO 2H
CH 2OH

2(R), 3(R)-Dihydroxy 2(S), 3(R), 4(R), 5-


succinic acid Tetrahydroxy- pentanal

H 3C

OH H
H
H
OH
CH3

Cyclohexanediol-1(R), 1(S),3(S)-Dimethyl
2(S) or meso- cyclohexane
cyclohexanediol-1,2

Chapter No. 7 : Concept of Chirality (Stereochemistry) 56


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STEREOCHEMISTRY

QEUSTIONS ASKED IN SET EXAMINATIONS

1) Natural cholesterol has 8 chiral centres. It can therefore exists as 28 i.e. 256 possible
isomer. The number of diastereomers of natural cholesterol are

OH H
H3C

H H Cholesterol

OH

A) 64 B) 128
C) 254 D) 255
2) The configuration of the compound shown below is

Cl

H3 C OH
OH
H

A) 2 R, 3 E B) 2 S, 3 E
C) 2 R, 3Z D) 2 S, 3 Z
3) For the two pairs of compounds given below, choose the correct statement
COOH COOH COOH COOH
HO H H OH HO H H OH
& &
H OH H OH HO H H OH
CH 2OH CH 2OH CH2 OH CH 2OH

(i) (ii)
A) Pair (i) is enantiomeric while pair (ii) is diastereomeric
B) Pair (i) is diastereomeric while pair (ii) is enantiomeric
C) Both pairs are diastereomeric
D) Both pairs are enantiomeric.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 57


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4) In the resolution of 1-phenylethylamine using [S] - () maleic acid, the compound obtained
by recrystallization of the mixture of the diastereomeric salt is [R] - 1 - phenylethyl ammonium
- [S] - maleate. The other component of the mixture is more soluble & remains in solution.
The configuration of the more soluble salt is-
A) [S] - 1- phenylethylammonium - [S] - maleate
B) [S] - 1 - phenylethylammonium - [R] - maleate
C) [R] - 1 - phenylethylammonium - [R] - maleate
D) [R] -1 - phenylethylammonium - [S] - maleate
5) The chiral molecule among the following are,

O
CH3 O
H OH

H OH

CH3 CH3
CH3

(i) (ii) (iii)


A) All three B) (ii) & (iii)
C) (i) & (ii) D) Only (ii)
6) The configuration of the compound shown below is :
CHO
H OH

H OH
CH2 OH

A) 2S, 3S B) 2S, 3R
C) 2R, 3S D)2R, 3R

Chapter No. 7 : Concept of Chirality (Stereochemistry) 58


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7) Choose the correct statement regarding the compounds shown below:

H CH3
CH3
Br H C

H CH3 C
Br HOOC H

(I) (II)
A) Both can be resolved B) Both can not be resolved
C) Compound (i) can be resolved but compound (II) can not be resolved as it has a plane
of symmetry passing through the olefinic carbons & also through all three substituents.
D) Compound (II) can be resolved but compound (I) can not be resolved as it has plane
of symmetry after rotation of lower carbon by 120o .
8) The absolute configuration of the comp given is :

CH2 OH

H3 C
C2H5

H C OH

CH2OH

A) 2S, 3E B) 2S, 3Z
C) 2R, 3E D) 2R, 3Z
9) Choose the correct relation of (ii) & (iii) with (i)

CH3 CH3 CH3

CH3 CH3 CH3


( i) ( ii ) ( iii )

A) Both (ii) and (iii) are enantiomers of (i)


B) Both (ii) and (iii) are diastereomers of (i)
C) Compound (ii) is a diastereomer of (i) while (iii) is an enantiomer of (i)
D) Compound (ii) is an enantiomer of (i) while (iii) is a diastereomer of (i).

Chapter No. 7 : Concept of Chirality (Stereochemistry) 59


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10) The geometry of the two double bonds in the given molecule is
Cl
COOH
H3 C
CHO CH3

Br

A) 2Z, 5Z B) 2Z, 5E
C) 2E, 5E D) 2E, 5Z
11) Chair form of cyclohexane has got these many gauche interactions:
A) 6 B) 2
C) 12 D) 0
12) Menthol has three asymmetric centres. How many epimers (E) and diastereomers
(D) are possible for it?
A) E3 ; D8 B) E3 ; D6
C) E1 : D8 D) E2 ; D6
13) In the compound shown below the geometry of the two double bond is:
CH 3 CH 2Cl
H3 COOC CHO

CH 2OH CH 2SH

A) 2Z, 5Z B) 2Z, 5E
C) 2E, 5E D) 2E, 5Z
14) -methyl-D-glucoside has five asymmetric centres. How many epimers (E) and
diastereoisomers (D) are possible for this molecule ?
HO

O O Me
HO
HO OH
A) E-5 ; D-30 B) E-5 ; D-31
C) E-4 ; D-32 D) E-4 ; D-30

Chapter No. 7 : Concept of Chirality (Stereochemistry) 60


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15) The chair form of cyclohexane has lower enthalpy than boat form because the boat has

4
1

2 3

6 5

A) The bowsprit flag pole interaction.


B) Eclipsing interaction at C1 /C2 and C4 /C 5
C) Both bowsprit flagpole interaction & eclipsing interactions C1 /C2 and C4 /C5
D) Both bowsprit flagpole interactions & eclipsing interactions at C2 /C3 and C5 /C6 .
16) The specific rotation of a molecule in a 5 cm polarimeter tube is +2o . What will be its
rotation in 10 cm. tube?
A) -40 B) 200
C) +40 D) -20
17) Select the appropriate stereochemical relationship among the following two
compounds.
CH3 CH3

And
OH

OH

A) Structural isomers B) Cis-trans isomers


C) Conformational isomers D) R & S isomers.
18) The compound shown below on treatment with base will

CH 3

CH3

H O CH 3

A) Undergo equilibrium B) Be recovered unchanged


C) Undergo epimerisation at C-5 D) Undergo epimerisation at C-7.

Chapter No. 7 : Concept of Chirality (Stereochemistry) 61


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19) Choose the correct configurational nomenclature for the following molecule:

CHO

H C OH

HO C H
H C OH
CH 2OH

A) 2R, 3S, 4S B) 2S, 3R, 4S


C) 2R, 3S, 4R D) 2R, 3R, 4S
20) Axial methyl group is less stable 1.8 kcal/mol than the equatorial counterpart due to 1,3-
diaxial interactions between CH3 and H
CH3 CH3
CH 3

For the given molecule, the energy estimated will be,


A) 3.6 kcal/mol B) More than 3.6 kcal/mol
C) 5.4 kcal/mol C) More than 5.4 kcal/mol
21) The correct statement regarding the compounds shown is
COOH

H OH
H 3C C 2H 5
HOOC H
H COOH
OH

(I) (II)
A) Both can be resolved
B) Both cannot be resolved
C) Compound (I) can be but (II) cant be resolved as it has plane of symmetry passing
through both olefinic carbons and all four substituent on these carbons.
D) Compound II can be but (I) cant be resolved as it has plane of symmetry after
rotation of lower carbon by 1200

Chapter No. 7 : Concept of Chirality (Stereochemistry) 62


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22) In the compound shown the configuration of the three double bonds is

CHO

CH 2 CH3

A) 2E, 6E, 9E B) 2Z, 6Z, 9E


C) 2E, 3Z, 9E D) 2Z, 6Z, 9Z.

23) Predict the relation between following two pairs


CH3 CH 3 CH3 CH 3
HO H H OH HO H OH H
& &
OH H H OH HO H H OH
Ph Ph Ph Ph

(I) (II)
A) Both pairs are enantiomeric
B) Both pairs are diastereomeric
C) Pair (i) is enantiomeric while pair (ii) is diastereomeric.
D) Pair (i) is diastereomeric while pair (ii) is enantiomeric.
24) Natural cholesterol on hydrogenation affords cholestanol as one of the product.

H H

HO
H

As this compound has nine asymmetric centre it can exists as 29 i.e.512 possible
isomers. The number of diastereomers of cholestanol are
A) 128 B) 256
C) 510 D) 511

Chapter No. 7 : Concept of Chirality (Stereochemistry) 63


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25) The configuration of the compound shown below is


HO

H3 C H

A) 1R ; 3R B) 1S ; 3S
C) 1R ; 3S D) 1S ; 3R

26) The chiral molecule/s among the following are


(i) 1,1-dimethylcyclopropane
(ii) cis- 1, 2-dimethylcyclopropane
(iii) trans1, 2- dimethylcyclopropane.
A) All three B) (ii) and (iii)
C) Only (ii) D) Only (iii)
H CHO

Cl C C H
27) The fischer projection of
HOOC Cl

CHO CHO
Cl H Cl H
A) Cl H B) H Cl
COOH COOH

COOH CHO
H Cl H Cl
C) H Cl D) H Cl
CHO COOH

28) (S)-2-chloro-2 ethyl pentanoic acid is represerted as :


Pr Pr

A) Cl COOH B) Et Cl
Et COOH
Et Et

C) Cl Pr D) Pr COOH
HOOC Cl

Chapter No. 7 : Concept of Chirality (Stereochemistry) 64


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29) The correct configuration of the double bonds at C2 , C4 & C6 in the following compound
is given by-
H3 C Cl H CH 3

COOH
Ph
A) 2(Z), 4(Z), 6(E) B) 2(Z), 4(E), 6(Z)
C) 2(Z), 4(E), 6(E) D) 2(E), 4(Z), 6(E)

CH 3
H Cl

30) Ph Cl can be represented by:


CH 3

CH 3 CH 3
H3C Cl Cl Ph

A) B)
Cl H Cl H

Ph CH 3

Cl CH3
H3 C H H 3C Cl

C) D)
Cl CH3 H Cl

Ph Ph

Chapter No. 7 : Concept of Chirality (Stereochemistry) 65


Notes for NET & SET - Chemical Sciences

31) Which one of the following is optically inactive?


Cl H H Cl

A) B)
H Cl Cl H

Cl
Cl Cl

H
C) D)
H
H H
Cl

32) How many steroisomers are possible for estradiol having the following structure?

OH
CH3 H

H H

HO

A) 5 B) 32
C) 16 D) 10
CH 2CH 3

CH3 (CH2)3 C OCOCH3


33) When optically active is hydrolysed with aqueous acid
CH 3

it would give:
A) (-) alcohol B) (+) alcohol
C) () alcohol D) n-octanol

Chapter No. 7 : Concept of Chirality (Stereochemistry) 66


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34) Choose the correct geometrical relationship between various groups in the given molecule:

Br Cl

A) C1 and Br trans; Cl & i-Pr trans; Br & i-Pr trans


B) Br & i-Pr cis; Cl & i-Pr- trans; Br & Cl trans
C) Cl & Br - cis; Cl & i-Pr (trans); Br & i-Pr cis
D) Cl & Br - trans; Cl & i-Pr cis; Br & i-Pr cis.

35) Select the correct geometry of the two double bonds in the following molecule:
CHO I
OCH3
H 3C

Cl CH 3

A) 2Z, 5Z B) 2E, 5E
C) 2E, 5Z C) 2Z, 5E
36) The specific rotation of a compound measured in a 5 cm polarimeter tube is +20 at
the given concentration, temperature & wavelength. Its specific rotation measured
in 10 cm tube under similar condition will be
A) +4 B) -4
C) -2 D) +2

STEREOCHEMISTRY
Answer Key

1) C 2) C 3) B 4) A 5)D 6) A 7) C
8) A 9) C 10) C 11) D 12) A 13) C 14) A
15) D 16) D 17) B 18) C 19) C 20) C 21) C
22) B 23) C 24) C 25) C 26) D 27) D 28) B
29) A 30) D 31) C 32) B 33) C 34) D 35) C
36) D

Chapter No. 7 : Concept of Chirality (Stereochemistry) 67